Method of treating shaped articles with betaine-type polymers and the articles thereby obtained

ABSTRACT

SHAPED ARTICLES, MORE PARTICULARLY FABRICS OF VARIOUS FIBERS, ESPECIALLY COTTON AND/OR HYDROPHOBIC SYNTHETIC FIBERS, E.G., OF LINEAR POLYESTERS (SUCH AS OF POLYETHYLENEGYLCOL TEREPHTHALATE) ARE TREATED WITH POLYMERS OF BETAINES OR SULFOBETAINES OR COPOLYMERS THEREOF WITH OR WITHOUT ACRYLIC ACID AND/OR AN ACRYLIC ESTER, SUCH AS METHYL ACRYLATE-PREFERABLY THE TREATING COMPOSITION ALSO CONTAINS AN AMINOPLST CONDENSATE CAPABLE OF IMPARTING CREASEPROOFING, WINKELPROOFING, AND DURABLE PRESS CHARACTERISTICS ON CURING WITH AN ACIDIC CATALYST. THE PROCESS AND TREATED FABRICS ARE CLAIMED.

3,671,305 METHOD OF TREATING SHAPED ARTICLES WITH BETAINE-TYPE POLYMERSAND THE ARTICLES THEREBY OBTAINED Albert B. Brown, Warrington, and FrankJ. Parkhill, Elkins Park, Pa., assignors to Rohm and Haas Company,Philadelphia, Pa. N Drawing. Filed Jan. 30, 1970, Ser. No. 7,268 Int.Cl. D06m 15/52, 15/54 US. Cl. 117-1383 F 10 Claims ABSTRACT OF THEDISCLOSURE DESCRIPTION OF THE INVENTION This invention concerns thetreatment of shaped articles, such as films, sheets, plates andfilamentary materials of a hydrophobic nature so as to give them adurable, hydrophilic, antistatic, antisoiling and soil-releasing finish.

Hydrophobic materials, when'formed into shaped articles of varioustypes, tend to accumulate static charges. These charges are particularlyevident in the preparation of fibers and the subsequent manufacture intotextile articles. As a result of formation of these static charges, thematerials have been found unsuited for certain purposes and somewhatunsatisfactory for garments. Therefore, it has been desirable to providea treatment for hydrophobic materials which would dissipate the staticcharges, but which would not subsequently impair such criticalproperties of the garment as tensile strength, flexibility, elongation,resistance to chemical, bacterial, and fungal agencies, and dyeability.It is also important to give the textiles a hydrophilic surfaceparticularly in fabrics used in the manufacture of undergarments, forinstance, where rapid transmission of perspiration is an asset.

One object of this invention is to provide a finish for hydrophobicshaped articles which does not alter the basic physical properties butgives them an antistatic hydrophilic surface. Another object is toprovide a durable antistatic finish for textile and other shapedproducts. A further object of the invention is to bond an amphotericpolymer to the surface of a shaped article while at the same timecausing partial chemical reaction to occur which insolubilizes thepolymeric coating without destroying its hydrophilic characteristics. Astill further object of the invention is to provide wettable finishesfor textile products, which finishes are further characterized bypossessing antisoiling and soil-releasing properties. Addition objectswould be apparent from the disclosure contained herein.

Fabrics treated in accordance with the present invention demonstrate theability of reducing or preventing pick-up of oily dirt duringlaundering, and also providing release of soil during cleaning,.especially laundering. These are desirable properties, particularly inregard to the soiling properties such as are encountered with fabricscomprising polyester-type materials. While we do not desire to be boundby any theory concerning the mechanism of the United States Patent 03,671,305 Patented June 20, 1972 'ice coatings of this invention, thisantisoiling property which is imparted to hydrophobic materials such aspolyesters is probably associated with a certain degree of substantivityof these fibers for oils. The hydrophilic layer of our polymeric betainecoating prevents the deposition of oily dirt either by charge effect ordegree of polarity.

In accordance with the present invention it has been found that theseimproved properties are obtained by the application to the shapedarticles, such as textile fabrics, of a polymer containing units of apolymerized betaine of the formula n is zero or an integer having avalue of 1 to 10,

R is H or methyl,

A is an alkylene group having 2 to 6 carbon atoms, at

least two of which extend in a chain between the quaternary nitrogenatom and the adjoined Z radical when n is 0, but when n is 1 to 10, A isa (C -C alkylene group having at least 2 carbon atoms extending in achain between 0 atoms or between an 0 atom and the adjoined N atom or Zradical,

R is (C -C alkyl,

R is (C -C alkyl, or

R and R may together form with the N atom a 5- to 6-atom ring, in whichthe atoms are C, N, or 0, such as the morpholino, piperidino, andpiperazino groups,

A' is a divalent saturated aliphatic hydrocarbon radical, such asalkylene, having 1 to 4 carbon atoms, and

O R is iiwherein m is 1 or 2.

While the monomers just defined do not all fall within the strictdefinition of betaines, they can be referred to as of betaine-type byvirtue of the quaternary ammonium nitrogen atom which is substituted bya carboxyl-containing radical and the fact that they form an inner saltas is indicated in Formula I hereinabove. For convenience, thesecompounds may sometimes be referred to as a betaine, a betaine-typecompound or as an inner salt of the N-(Z-carboxyethyl) quaternary of thetertiary amine from which the compound is derived; for example, theexpression N(2-carboxyethyl) inner salt of dimethylaminoethyl acrylate(DMAEA) may be applied to the product obtained by reaction of acrylicacid with DMAEA. Similarly, the polymers used herein may be referred toas a betaine polymer, a betaine-type polymer, or a polymer of a betaine,a betaine-type monomer of an inner salt of the N-(Z-carboxyethyl)quaternary of the tertiary amine monomer from which the monomer isderived.

The monomeric betaines may be made by the reaction of tertiary amines ofthe formula R (II) wherein the symbols are the same as designated above,with a lactone of the formula CHz-CHC=O or derivatives of the lactone,having 3 to 7 carbon atoms in which one to'four of the hydrogen atomsare replaced by alkyl groups having one to four carbon atoms. Examplesof compounds of Formula II include;

( fi-acryloxyethyl dimethylamine dimethyl fl-methacryloxyethyl amine(acryloxyethoxyethyl) diethylamine (acryloxyethoxyethoxyethyl)dibutylamine dimethyl [methacryloxyethyl (oxyethyl) amine(fi-methacryloxypropyl dimethylamine 8- ii-methacryloxypropyloxy propyl]dimethylamine N- dimethylaminoethyl) acrylamide,

N- dimethylaminoethyl methacrylamide,

N- (dimethylaminopropyl) acrylamide,

N- (dimethylaminopropyl methacrylamide.

Examples of S-lactone compounds of Formula III include:

p-propiolactone, fl-butyrolactone, fi-valerolactone,fi-iso-valerolactone, u-methyl-B-propiolactone, a-ethyl-B-propiolactone,isopropyl-fi-propiolactone, [5isopropyl-p-propiolactone,ii-methyl-B-valerolactone.

' The reaction may be carried out in aqueous solution (in which case thequaternary ammoniumhydroxide is formed by hydrolysis of the betaine) inthe presence of an inert organic solvent, or simply by admixing the tworeactants in the absence of any solvent or diluent. Preferably, an inertorganic solvent is utilized since stirring of the reaction mixture andheat removal is thereby facilitated, and the tendency for thebeta-lactone to polymerize is repressed. The specific nature and amountof the solvent used, if any, are not all critical since any polar ornon-polar organic solvent may be used so long as it is capable ofexisting in the liquid state, and is substantially inert to thereactants under the conditions used. It is desirable that the solvent bevolatile, preferably that it have a boiling point below 150 C. since itcan then be more readily recovered and reused in the process. Specificinert solvents which are effective include benzene, toluene, pentanes,hexanes, and other liquid saturated aliphatic or aromatic hydrocarbons;chlorinated liquid derivatives of such hydrocarbons such aschlorobenzene and ethylene dichloride; liquid ethers such as diethylether, dipropyl ether, etc.; liquid esters such as methyl acetate, ethylacetate, methyl propionate and the like; liquid organic nitriles such asacetonitrile, propionitrile, benzonitrile, etc.; and liquid ketones suchas acetone, methyl ethyl'ketone, etc. Liquid alcohols are alsosubstantially inert to the reactants under the preferred conditions ofthe reaction (that is, at temperatures of 30 to 60 0.), despite the factthat alcohols do react with beta-lactones under other conditions.Accordingly, such alcohols may be employed as solvents if desired,examples of suitable alcohol solvents being methanol, ethanol, ethylenecyanohydrin, ethylene chlorohydrin, and especially tertiary alcoholssuch as tertiary butanol, and the like.

. No special reaction conditions are necessary in order to carry out thereaction. The quantities of beta-lactone and tertiary amine employed arenot critical but it is generally preferred to use equimolecularproportions of lactone and amine or an excess of the amine, for example,from 1 to 2 moles of amine for each mole of lactone.

The reaction is preferably carried out at atmospheric pressure and at atemperature in the range of 30 C. or lower to 100 C. or even higher,more preferably at 0 C. to 50 C. The reaction is exothermic andliberates heat, hence, it is unnecessary to supply heat externally butit often is desirable to cool the reaction mixture in order to maintainthe preferred temperature. However, other temperatures and pressures maybe used provided the 4 reactants are maintained in the liquid conditionduring the reaction.

In carrying out the reaction of this invention, it is generallypreferable to add the amine to a solution of the beta-lactone in wateror one or more of the solvents listed hereinabove at such a rate about/2 to 5 hours are required for addition of the entire amount of amine,and with continued agitation of the solution during the addition.However, the beta-lactone may be added to a stirred solution of theamine in an organic solvent, or water, if desired, without affecting thefundamental course of the reaction to give a quaternary amine or anyother procedure for bringing the reactants together in an organic mediumat 30 C. to 60 C. is also effective. Slow addition of one reactant tothe other, and agitation of the solution during reaction are bothhelpfulin maintaining the desired temperature (since the reaction is exothermicand may generate sufficient heat to cause the temperature to riseconsiderably above 60 C. if heat transfer is not efficient) but are notcriticalexpedients in themselves. The time during which the reactantsmust be left incontact is likewise not critical and will depend upon thetotal quantities of reactants being used; in general the reaction isquite rapid and is complete, as evidenced by cessation of heatevolution, within a short time after all of the two reactants have beenbrought into efficient contact with each other.

As the reaction proceeds, the product usually separates from thereaction mixture in the form of crystals which may be easily separatedfrom unreacted amine and betalactone as well as the solvent, if any,simply by filtering. A product of high purity is obtained byrecrystallizing the solid product from an organic solvent such asethanol or methanol. However, other conventional methods of separationmay also be used without seriously affecting the yield of the productobtained.

The monomeric sulfobetaines and their preparation are disclosed in HwaSer. No. 316,163, filed Oct. 14, 1963,

' now Pat.' 3,497,482. As disclosed therein, they may be prepared byreacting an amine of the Formula II above with either a sultone ofFormula IV or a cyclic sulfonate of Formula V:

AO O/ \O (1V) the symbol A being as defined hereinbefore.

Examples of the alkane sultones of Formula IV include 1,2-ethanesultone, 1,3-propane sultone, 1,4-butane sultone, and thealkyl-substituted sultones such as l-methyl-l, 3-propane sultone.

Examples of the cyclic sulfates of Formula V include ethylene sulfate,l-methyl-ethylene sulfate, and 1,2-dimethylethylene sulfate.

The tertiary amine and the cyclic sulfo compound (of either Formula IVor Formula V) are generally used in equimolar proportions although awide variation from equimolar proportions is permissible.

However, there is no need, and generally no advantage is obtained byusing an excess of either reactant over the equimolar equivalent of theother reactant. The reaction may be effected merely by mixing the tworeactants in bulk, the reaction occurring at room temperature ortemperatures below or above room temperature. For example, 10 C. up toC. or higher (depending on the boiling point of the solvent used) may beemployed. Generally, temperatures from 30 to 70 C. are preferred. Atelevated temperatures it is frequently desirable to use a polymerizationinhibitor to prevent polymerization of the monomer produced during itspreparation. Instead of gradually mixing the two reactants in bulk, theymay be mixed in any suitable solvent of inert character (in regard tothe reaction) such as water, or such organic solvents as hydrocarbons(octane, heptane, benzene, toluene, xylene); esters such as ethylacetate, butyl acetate, amyl acetate, B-hydroxyacetate, the methyl etherof p-hydroxyethyl acetate, 2-hydroxyethoxyethyl acetate; ketones such asacetone and methyl isobutyl ketone; nitriles such as acetonitrile;chlorinated hydrocarbons such as ethylene dichloride, chloroform, andcarbon tetrachloride; ethers such as dioxane, ethyl ether, methylisopropyl ether, and ethyl butyl ether, and alcohols having from 1 to 6carbon atoms such as ethanol, methanol, isopropanol, tert-butanol, andcyclohexanol.

The products are generally crystalline solids which precipitate from thereaction medium except when that medium is water, an alcohol, or amixture thereof. The product may be recovered from the solution in thelatter case by evaporation of solvent.

An advantageous method of producing monomeric betaines is that disclosedand claimed in an application for U.S. Pat. Ser. No. 856,822, filedSept. 10, 1969, of Norman Shachat, Richard Haggard and Sheldon Lewisentitled Method of Producing Betaines,-Monomers and Polymers ContainingBetaine-Type Units and Novel and Useful Copolymers Thereby Obtained.This method involves the reaction of an amine of Formula II above witheither acrylic acid or with a (C -C alkyl acrylate and water, whichreaction when the alkyl acrylate is used, liberates a (C -C alcohol andthe betaine.

Polymers containing betaine-type groups may then be prepared from themonomeric betaines and sulfobetaines thus obtained in conventional ways,using, for example, a free-radical catalyst. The polymerization may beeffected as a solution polymerization, a suspension polymerization, anemulsion polymerization, or a precipitation polymerization. Any suitablefree-radical catalyst may be employed, and especially water-solubletypes when the polymerization is to be effected inaqueous media. In anaqueous system, whether involving solution or emulsion polymerization,it is desirable to operate at a pH of about 1.5 to 3.5, e.g. byadjustment with an acid, such as sulfuric acid. Examples of catalystinclude hydrogen peroxide, ammonium persulfate, or an alkali metalpersulfate. A redox system using such a persulfate with a reducing agentsuch as sodium hydrosulfite is quite useful. In solution systemsinvolving organic solvents for the monomers and polymers, a free-radicalinitiator soluble in the particular medium may be employed such asbenzoyl peroxide, lauroyl peroxide, tert-butyl peroxide, orhydroperoxide. The usual amounts of initiator may be employed such asfrom 0.1% to 6% on the weight of the monomer, and in the redox systemsthe persulfate may be employed in amounts of about 0.05 to 1% or so, inconjunction with about 0.05 to 1% of sodium hydrosulfite. Chain-transferagents and other molecular weight regulators may be used.

For imparting antistatic and/or soil-release properties to shapedarticles, such as films or textiles respectively, a homopolymer orcopolymer of a betaine of Formula I can be applied, and the applicationmay be made in conjunction with a thermosetting aminoplast textile resinfor enhancing durability of the antistatic and/or soil-release effects.

Besides direct polymerization of one or more betaines of Formula I withor without one or more other monomers, especially monoethylenicallyunsaturated monomers having a terminal group H C=C the polymers that areuseful in accordance with the invention may be made from homopolymers orcopolymers of an amine of Formula II above by reacting it with asuitable reagent, such as a lactone of Formula III above, a sultone ofFormula IV above, a cyclic sulfonate of Formula V above, or an alkalimetal salt of a haloalkanoic acid of the following Formula VI:

wherein X is chlorine or bromine, R is the same as defined hereinabove,and M is an alkali metal, such as sodium, potassim, or lithium.

Examples of compounds of Formula VI are:

sodium a-chloroacetate potassium u-bromoacetate sodiumB-chloropropionate lithium 4-chlorobutyrate sodium a-ChlOIO-ot-IIlGthYlpropionate sodium wchloropropionate This quaternization reaction may beeffected in a polar solvent such as water, ethanol, acetonitrile,dimethylformamide, or glycol ethers such as ethoxyethyl hydroxyethylether or mixtures of one of these solvents with benzene or toluene at atemperature of 10 to 100 C. for a period of about two to twelve hours.The alkylating agent of Formula VI may be used in a quantity that ismolarly equivalent to the total number of amine groups in the polymer toquaternize all of such groups. However, when there is more than 5percent by weight of the monomeric units containing a quaternizableamine group, it is unnecessary to quaternize all of such amine groupsand the amount of quaternizing agent may be less than the amountrequired to quaternize all of the amine groups in the polymer providedsufficient is used to provide 5 weight percent of quaternized monomericunits having Formula I in the final polymer.

Alternatively, the polymer or copolymer of an amine monomer of FormulaII may be reacted with acrylic acid or with a (C C alkyl acrylate,preferably methyl acrylate, and water in the manner described in theaforementioned application Ser. No. 856,822. As in the quaternizationreactions described in the preceding paragraph, the reaction withacrylic acid or with an acrylic ester and water may involve sufficientof the latter reagent to convert all of the amine units intobetaine-type units in the polymer or only a portion thereof provided theresulting polymer contains at least 5 weight percent of the units ofFormula I above.

The molecular Weight of the betaine polymers should be at least about5,000 and is preferably at least 10,000. It may be up to 100,000 or evenup to 1,000,000 or several million in some instances, especially in thecase of copolymers.

In accordance with the present invention, polymers that produceimprovement in durability of soil release, anti-static and/orfungistatic properties when applied in conjunction with a thermosettingtextile resin of aminoplast type are copolymers of (a) about 5 to 100%by weight of a betaine of Formula I above, (b) 0 to by weight of annip-monoethylenically unsaturated acid and 0 to 95 by weight of othermonoethylenically unsaturated monomers having a group of the formula HC=C such as a (C -C alkyl acrylate, methyl methacrylate, acrylonitrile,styrene, vinyltoluene, methacrylic acid, itaconic acid, maleic acid,fumaric acid, the mono (C -C alkyl esters of itaconic acid, maleic acid,or fumaric acid, acrylamide, methacrylamide, the N-methylol derivativesof the last two monomers, hydroxyethyl acrylate or methacrylate,hydroxypropyl acrylate or methacrylate, hydroxyl vinyl ether or sulfideor mixtures of any two or more of such comonomers. However, whenrelatively highly hydrophobic monomers, such as styrene, vinyltoluene,and acrylonitrile are used as comonomers, it is preferable that thecopolymer contain at least 10% to 20% of the betaine-type monomers or ofa mixture of the betaine-type monomer and acid monomer. While soilrelease is obtained when water-insoluble emulsion copolymers are used,it is preferred that the copolymers have some water-solubility for easeof application and optimum effect on soil release effect. Preferredcopolymers with respect to the imparting of soil-release properties ontextile fabrics generally, and especially those containing polyesterfibers, are those containing copolymerized therein about 20 to 60% byweight of at least one Formula I betaine, 15 to 50% by Weight of acid,such as acrylic acid and/or methacrylic acid, and to 60% by weight of atleast one other monomer, such as methyl acrylate.

Application of the betaine-type polymers, with or Without an aminoplast,to provide antistatic, fungistatic, soilrelease, and/or anti-soilingproperties is generally beneficial on all types of fibrous materials,including fibers or fabrics of the natural fibers, such as cotton, silk,linen, and wool, and of the artificial fibers, such as regenerated cellulose (viscose or cupramonium cellulose), cellulose esters, e.g.,cellulose acetate, casein polyamides or nylons of all types,acrylonitrile polymers including its copolymers, (e.g., with vinylacetate, methyl acrylate, and/or vinylpyridine), vinylidene chloridepolymers including its copolymers with vinyl acetate, methyl acry-late,acrylonitrile and/ or acrylic acid, methacrylic acid, or itaconic acid,vinyl chloride polymers including its copolymers with vinyl acetate oracrylonitrile.

The present invention is particularly directed to a process forimparting soil release and durable press characteristics to a textilematerial, especially one comprising linear polyester fibers whichcomprises applying thereto an aminoplast textile resin, a textile resincatalyst, and a betaine polymer which is stable under the conditions ofapplication, and curing the textile resin. The polymer comprises atleast 5 weight percent of betaine-type units, and the proportions ofbetaine polymer solids deposited on the textile material is from 0.25%to 30% and, preferably, from 0.5 to by weight, based on the dry weightof the textile material.

The amount of soil release polymer in the pad bath may vary from about2.5 to 40%. Preferably, the polymer solution or dispersion is adjustedto pH 4-5 with a mineral acid, such as H 50 or base, such as NaOH,before preparation of the pad-bath solution or dispersion, oralternatively, the final pad bath solution or dispersion containingaminoplast, soil-release polymer, catalyst, and, if desired, softenerand other textile modifiers is adjusted to pH 4-5 with mineral acid orbase. If the polymer contains a considerable proportion of such highlyhydrophobic units as styrene, vinyltoluene, or acrylonitrile, the pH ispreferably above 5 such as from about 5.5 to 8.

Soil removal ability is improved on any organic substrate, especiallythose comprising hydrophobic fibers, such as linear polyester fibers,when the betaine polymer is applied thereto. Suitable substratescomprising polyester fibers, which should not be considered as limiting,may be prepared from paper, synthetic polymers, cotton, wool, mixturesof the above, etc. Products made from these materials include withoutlimitation, wall paper; synthetic wall coverings; textile fabric wallcoverings; lamp shades; automobile seat covers; automobile upholstery,e.g., door panels, overhead liners, etc.; upholstery for furniture;clothing; apparel accessories, e.g., ties, fabric belts, scarves, hats,etc.; canvas products, e.g. tents, folding cots, etc.; draperies; throwpillows; hassocks; sporting goods; fabric garment bags and luggage;fabric handbags; fabric shoes or shoes made from synthetic materials;linens; book covers; mattress covers; stuffed toys; hammocks; deckchairs, etc.

The term textile material comprising polyester fibers comprisespolyester fibers with other fibers within the above definition, e.g.,cotton, paper, linen, jute, flax, regenerated cellulose fibers,including viscose rayon, in the form of staple, yarn and fabrics. Thisinvention is directed primarily and preferably to polyester andcellulosic containing textile fabrics either knitted, woven, ornonwoven, but preferably woven. However, the advantages of thisinvention can be achieved by treating the fibers, yarns, or threadsemployed to produce these fabrics.

Moreover, and more specifically, the process of the present invention ispreferably used for treating textile materials containing both polyesterand cellulosic and noncellulosic fibers, especially, if thenon-cellulosic fibers have minimum-care characteristics of their own.For example, the fabrics treated may be formed from a mixture ofpolyester, such as poly (ethylene terephthalate) and polyamide, such aspoly(hexamethylene adipamide), or acrylic fibers, such aspolyacrylontrile and copolymers containing at least about combinedacrylonitrile, cotton or rayon. It should be pointed out, however, thattextile material containing only non-cellulosic fibers such as thoselisted above is also within the scope of the present invention.

The soil-release properties of pure cellulosic fiber fabrics are muchbetter than those of synthetic fiber containing fabrics, e.g. polyesterfibers, in that, the synthetic fibers are generally hydrophobic and thusprevent the ingress of Water that is necessary for cleaning the fabricand also possess an electrical charge that attracts soil particles. Thepresent invention is therefore primarily directed to fabrics containinga substantial portion of synthetic hydrophobic fibers such as polyesterfibers.

An aminoplast textile resin is also applied with the polymer. Veryunexpectedly, it has been observed that when the textile resin and thebetaine polymer are both applied to the textile material followed bysubjecting the material to textile resin curing conditions, improvedsoil release is realized.

Hence, the present invention is also directed to a process for treatinga textile material by applying thereto an aminoplast textile resin, atextile resin catalyst and a film-forming synthetic betaine polymer,said polymer containing at least 5 weight percent betaine and effectingthe formation of a film around the fibers that make up the textilematerial While curing the textile resin.

The term textile resin according to the present invention includes bothmonomers and polymers which when applied to a textile material andreacted under proper conditions undergo polymerization and/orcondensation and are transformed to the thermoset state. Textile resinsthat may be employed when practicing the present invention are theaminoplast resins. These nitrogen containing resins when applied to atextile material in the presence of a catalyst at temperatures of fromC. to about 200 C. are transformed into the thermoset state. Theaminoplast resin condenses with the cellulose molecules and when vinylgroups are present in the aminoplast resin, it undergoes additionpolymerization with itself and also with the cellulose molecule ifirradiated. The cured textile resin on the textile material affords thetextile material a durable press and/or wrinkle resistantcharacteristic.

Exemplary of the aminoplast resins that may be employed according to thepresent invention are the urea formaldehydes, e.g., propylene ureaformaldehyde, di methylol urea formaldehyde, etc.; melamineformaldehydes, e.g., tetramethylol melamines, pentamethylol melamines,etc.; ethylene ureas, e.g., dirnethylol ethylene urea, dihydroxydirnethylol ethylene urea, ethylene urea formaldehyde, hydroxy ethyleneurea formaldehyde, etc., carbamates, e.g., alkyl carbamateformaldehydes, etc., formaldehyde-acrolein condensation products;formaldehyde-acetone condensation products; alkylol amides, e.g.,methylol formamide, methylol acetamide, etc.; acrylamides, e.g.,N-methylol acrylamide, N-methylol methacrylamide, N methylolN-methacrylamide, N-methylmethylolacrylamide, N-methylolmethylene-bis(acrylamide), methylene-bis (N-methylol acrylamide), etc.;haloethylene acrylamide; diureas, e.g., trimethylol acetylene diurea,tetramethylol acetylene diurea, etc.; triazines, e.g.,dimethylol-N-ethyl triazine, N-N' ethylene-bis dirnethylol triazine,halotriazones, etc.; haloacetamides, e.g.,N-methylol-N-methylchloroacetamide, etc.; urons, e.g., dimethylol uron,dihydroxy dirnethylol uron, etc.; and the like. Mixtures of aminoplasttextile resins are also within the scope of the present invention.

The amount of aminoplast textile resin applied to the fabric isprimarily determined by the ultimate use of garments or articlesprepared from the fabric. On durable press fabrics or garments, theamount of resin employed is preferably that which will afford goodcrease retention and flat dry properties while not adversely affectingthe hand. For the purposes of the present invention, the amount oftextile resin in the pad bath may vary between about 2 and 30%. Resinapplied to the fabric should bein the range of about 2 to 20% based onthe dry weight of the gabric and preferably in the range of about 4 to9% Catalysts employed Within the scope of the present invention dependupon the specific textile resin that is applied to the textile material.For instance, if the textile resin has a functional group that isreactive under acidic conditions, then an acid catalyst is used.Likewise, when a functional group is present that is reactive underalkaline conditions, then a base catalyst is used. Furthermore, bothacid and base catalysts may be used when both type functional groups arepresent in the textile resin. In this instance, the catalysts may beadded separately or together. When they are added together, one must bea latent catalyst, i.e., one that will not initiate its reaction duringhe opposite type reaction, but may be activated subsequently underproper caalytic conditions.

The catalysts useful in activating the acid or base reactive groups arethose conventionally used to activate the reaction of textile resinscontaining the same group for reaction with hydroxy groups of cellulose.Preferably, latent acid or base acting catalysts are utilized, that is,compounds which are acidic or basic in character under the curingconditions. The most common acid acting catalysts are the metal salts,for example, magnesium chloride, zinc nitrate and zinc fluoborate andthe amino-salts, for example, nonoethanol-amine hydrochloride andZ-amino- Z-methyl-propanol nitrate.

The base acting catalyst preferably is a compound which does notinitiate substantial reaction between the base reactive group andhydroxy groups of cellulose under normal acid conditions, but doesinitiate substantial reaction under prescribed conditions, such aselevated temperature or some other activating means, as through use ofanother chemical compound. For example, an alkali metal sulfite can bepadded onto the fabric and be decomposed into strongly basic alkalimetal hydroxide by including small amounts of formaldehyde in the steamused for curing.

The latent base acting catalyst utilized herein preferably comprisesalkali-metal salts, such as alkali-metal carbonates like sodiumcarbonate, which is neutral to mildly alkaline, for example, pH of about8.5 on the fabric but decomposes at temperatures in excess of about 80C. to form the stronger base sodium oxide which will initiatesubstantial reaction at the elevated temperatures utilized duringcuring. Sodium carbonate may be utilized if desired since the pH in thefabric produced by this compound in normal conditions is generallyinsutficient to initiate the desired degree of reaction under normaltemperature conditions.

If fabrics containing a base reactive group are maintained at pH levelsabove about 10, however, degradation occurs, so that essentially neutralor mildly alkaline catalysts are preferred when base reactive compoundsare utilized.

Additional base acting catalysts include potassium bicarbonate,potassium carbonate, sodium silicate, alkali metal phosphates, bariumcarbonate, quaternary ammonium hydroxides and carbonates for example,lauryl trimethyl ammonium hydroxides and carbonates and the like.

The amount of catalyst to be utilized is that conventionally used inactivating the reaction between textile resins and hydroxy groups ofcellulose, for example, up to about by weight of an acid acting catalystin the application bath with the preferred range being from about 1% toabout 7%. A preferred range for the base acting catalyst is again theconventional amount and is generally between about 0.2% to about 16%,preferably about 2 to 16%. The amount of catalyst to be utilized willfurther depend in part on the temperature at which the reaction isconducted and the amount of catalyst consumed in the reaction. Forexample, when base catalysts are utilized and if a highly acidic groupis released during the reaction, the amount of base applied to thetextile material should be at least sufficient to provide an excess ofbase in addition to that which is consumed by the highly acidic group.

The term soil release in accordance with the present invention refers tothe ability of the fabric to be washed or otherwise treated to removesoil and/or oily materials that have come into contact with saidmaterial. The present invention does not per se prevent the attachmentof soil or oily materials to the fabric, but hinders such attachment andrenders the heretofore uncleanable fabric now susceptible to asuccessful cleaning operation. While the theory is still somewhat of amystery, soiled, treated fabric when immersed in the detergentcontaining wash water experiences as agglomeration of the oil at thefabric surface. This water is basic in nature and it has been determinedthat soil release is best realized in wash water that is basic innature. These globules of oil are then removed from the fabric and riseto the surface of the wash water. This phenomenon takes place in thehome Washer during continued agitation, but the same effect has beenobserved even under static conditions. In other words, a strip ofpolyester/cotton fabric treated according to the process of the presentinvention and soiled with crude oil, when simply immersed in a detergentsolution will lose the oil without agitation. The oil just balls up onthe fabric, dislodges therefrom, and rises to the surface of thesolution.

An added feature of the present invention is the prevention of soilredeposition from the wash water. One of the greatest disadvantages ofthe synthetic polymers is the feature that even after removing the soilby washing, there is the continued danger that the soil will beredeposited onto the fibers from the Wash water before the garment isremoved therefrom. It has been observed that the soil release ability ofthe presently treated fabric diminishes after repeated washings. Evenafter the ability to remove soil from the fabric has diminished,however, the observation has been made that the prevention ofredeposition of soil from wash water remains potent. This phenomenonlikewise is unexplainable, but it has been established that thetroublesome soil is negatively charged and presumably there remainsenough acid on the fabric to repel the negatively charged soil.

Numerous of the substrates that may be treated according to the processof the present invention may not be feasibly removed from theirenvironment and Washed in a washing machine. Further, there are alsosubstrates that may be treated which when subjected to the action of awashing machine are adversely affected either in structure or in looks.Articles within these classes may still be easily cleaned in place orotherwise by scrubbing the soiled area lightly with a solution of acommercial detergent and water.

The soil release polymer of the present invention is capable of forminga film around the fibers that constitute the textile material. Softnessof the film is important, for if the film is too hard, the hand of thetextile material is adversely affected. Further the film must havehydrophilic properties and yet be relatively insoluble in water. Thefilm, if water soluble, would, of course, be easily washed from thefabric. Thus, it is ordinarily necessary that the soil release polymerhave a molecular weight of at least about 5000 but may be as low asabout 2000 to 3000 in some instances.

In summary, the shaped article, such as a textile fabric is treated withan aqueous solution containing (a) about 0.25 to 20% (preferably 0.5 to15%) by weight of the betaine or (sulfobetaine) polymer, (b) about 2 to20% by weight of an aminoplast, such as a ureaformaldehyde or melamineformaldehyde or N,N-ethyleneurea formaldehyde condensate, and (c) about/2 to 4% by weight, based on the weight of the condensate, of a catalystfor setting or curing the condensate. The treatment may be effected byspraying or immersion, such as in a textile pad at room temperature orup to 30 C. The treatment equipment, such as the pad, may be controlledto provide from 70 to 100% wet pick-up. The treated fabric may then bedried such as at room temperatures or at an elevated temperature up toabout 120 C. To cure the resin and set the composition, the drying ispreferably followed by a heating step, such as to about 130 to 200 C.for a period of /2 to 30 minutes, the longer times being used with lowertemperatures.

In using the betaine-type copolymers mentioned, the

betaine and/or acid u'nits therein cause the film on the treatedmaterials to swell without being substantially dissolved. In the case ofthe preferred copolymers this swelling is drastic, on the order of500'-1000%. It appears that the swelling action that occurs duringwashing in aqueous media virtually expels the dirt by mechanical actionfrom the intersticial spaces in the yarns of the fabric.

' To some extent, carboxylic acid groups, if any are present in the soilrelease polymer, contribute to durability of polymer to washing. Thismay be attributed to anhydride formation or hydrogen bonding betweenacid groups an adjacent polymer chain segments, or reaction of suchgroups with aminoplast resin. However, in many cases, it has been foundthat physical and chemical interaction of carboxylic acid groups alonedoes not provide satisfactory durability to washing. For example,fabrics (65/35 polyester/cotton blends) treated with synthetic acidemulsion polymers in accordance with US. Pat. 3,377,249 can be madewhich have an excellent (45 Deering Milliken Rating) soil releasingeffect which, however, endures only to washes. However, the treatment offabrics of the same type with preferred compositions of the presentinvention have resulted in excellent soil-releasing effects after asmany as to washes, and in many cases, the treated fabrics of the presentinvention have shown improvement in soil release even after as many as50 washes. This unusual durability to washing may be attributed to theinclusion of betaine units in the polymers used.

With the understanding that applicants do not intend to be limited toany particular theories of action, the following explanations forexcellent soil release and durability to Washing of polymers containingbetaine monomers are proffered. The betaine units, whether or not anaminoplast textile resin has been applied to the fabric with thepolymer, may have some bonding action, either chemical or physical, withthe fabric. This may be the result of ionic charges on the polymer chainthat may favor such adherence by an ionic linking to a fabric substratethat develops an electric charge in aqueous wash solution. Furthermore,polymer may be insolubilized by intraor intermolecular ioniccrosslinking between betaine units on adjacent polymer chain segments.In those copolymers which contain neutral or non-ionic monomers such asthe acrylic esters, in addition to betaine units, with or withoutacrylic acid units, the neutral and acid units, if any, apparently serveto dilute the concentration of betaine units within a given polymerchain. Such a dilution results in a lower probability of chargeinteraction between different betaine units and favors neutralization ofcharge by ion-pair formation within a given betaine unit, i.e.,

O A (two interacting [I betaine units) *N C Ha) zCHzCH: C O

-00 onior-monow or more probably B (one betaine unit) It appears thatthe most effective soil release requires controlled swelling andcontrolled gradual, though slow removal of the soil release agent fromthe fabric during washing periods.

By selecting the concentration of diluting monomer in the soil releasepolymer, the extent of swelling and the rate of removal is readilycontrolled, the ease of removal being gradually increased by increase ofthe proportion of diluting monomer units, and the extent of swellingbeing increased by increasing the proportion of betaine units and, ifany, of acid units. However, even when the release polymer contains fewor no diluting units, repeated washings in alkaline detergent solutionscause the slow and gradual breaking of the ionic bonds between polymerchain segments and the polymer, even though initially having lowswelling tendency, acquires the ability to swell satisfactorily, as aresult of washing during use. Thus, when fabrics are treated withpolymers low in diluting units (such as less than 10%), soil release mayinitially be of marginal character but gradually improves after thefabrics have been washed a number of times, especially if care is takento avoid severe soiling or staining during the early period of use;after two to ten 'washes, depending on the particular soil releasepolymer, excellent soil release is generally obtained.

Soil release polymers containing betaine and acrylic acid monomers arepreferably applied at an optimum pH which can be determined from thetitration curves of the polymers. There are two inflection points in thetitration curves. The first generally occurs in the pH 4-5 range forpolymers containing betaine of Formula I and corresponds to completeneutralization of any strong acid present used for polymerization, asWell as complete neutralization of the carboxylic acid groups of betaineunits. (The carboxylic acid groups of betaine units are generallystronger acids than acrylic acid.) The second inflection point occurs athigher pH and'corresponds to neutralization of acrylic acid in thecopolymer backbone. Optimum soil release and durability to washing isgenerally obtained when the polymer is applied in such a manner that thecarboxylic acid groups of the betaine units, but not those of acrylicacid, are neutralized. This generally corresponds to a pH range of 45.However, when the soil-release polymer contains relatively largeproportions of highly hydrophobic units, as of styrene, acrylonitrile,etc., the use of higher pH values, such as from 6 to 8, may bepreferred. Apparently, if betaine units are not neutralized prior towashing, the basicity of wash solutions is consumed first inneutralizing the acid groups of betaine units. These negatively chargedgroups immediately form ion pairs with positively charged nitrogenresulting in little additional net charge development on the polymerchain, and therefore, minimal electrostatic repulsion necessary fordrastic swelling of polymer and effective soil release. In such cases,excellent soil release is sometimes not obtained until the fabric hasbeen washed a number of times before severe soiling or staining. Eachsubsequent Washing results in increased ionization of polymer untilsatisfactory swelling is obtained. On the other hand, if polymer isapplied at too high a pH, two much acrylic acid is ionized beforewashing. Washing results in unnecessarily excessive swelling of polymerand rapid removal from the fabric substrate; initial soil releaseratings are excellent, but poor soil release is obtained after fabricsare Washed a few times.

In the illustrative examples which follow, the parts and percentages areby weight and the temperatures are in C. unless otherwise noted. Thefollowing procedure is the one used to evaluate the soil releaseproperties of a fabric. An air-dry, 7 in. x 6 in., sample is stainedwith four soils, each in a different location on the sample:

refined mineral oil (Nujol), used motor oil, spaghetti sauce (Ragu), andpepper sauce (Tabasco). These-materials are left on the fabric for 30min. The excess is then blotted and the fabric air-dried for 10 min. Thesamples are rinsed for 12 min. in cold water in the automatic washer toremove heavily caked-on soil and then'laundered as described in the nextparagraph with a 4 lb. ballast of terrycloth bath towels. The samplesare then tumble-dried at the hot setting of a home laundry dryer andvisually rated for soil release appearance using the Deering Millikenphotographic standards for comparative purposes (col. 16, lines 13-15,of U.S. 3,377,249). A rating of 1 indicates essentially no removal ndcomplete removal of soil; 4 to 5 is excellent, 3 to 4, good. The averagerating given is the average of the individual ratings of the four soiledareas.

The treated fabrics are washed once or repeatedly in an impeller-typeautomatic home laundry washer, each cycle with 16 gal. of water at 60C., one cup of anionic detergent (Tide), and a ballast of terryclothbath towels. After various numbers of washes, samples are removed forthe testing of or evaluation of soil release performance at thosestages, the results being summarized, for example, in Table I. In thisfashion, the durability of soil-release properties in the treatedfabrics are determined.

Example 1 (a) A mixture (about 23 parts) containing 49% of the betainewhich is the N-(Z-carboxyethyl) inner salt of dimethylaminoethylmethacrylate (DMAEMA), 31% of acrylic acid (AA) and of methyl acrylate(MA) is added to 80 parts of water containing about 0.25 part of sodiumisododecylphenoxypoly (40) ethoxy sulfate and is adjusted to a pH of 2.1with sulfuric acid. Then 0.047 part of ammonium persulfate and 0.025part of sodium hydrosulfite are added. The temperature rises and afterthe batch cools the product is a 21.3% solution of a copolymer of about49% of the specified betaine, 31% of AA and 20% of MA having a viscosityof 7800 cps. (Brookfield Viscometer, 60 r.p.m.). Sodium hydroxide isadded to adjust the pH to 4.5, the viscosity rising to 24,600 cps.

(b) A pad-b'atnsolution containing a durable-press aminoplast resin andthe soil-release polymer ust described is prepared by mixing reagents atthe following concentrations in water: 11% (solids)dirnethylol-dihydroxy-N, --N-ethylene urea (DMDHEU) (using a 45% aqueoussolution), 6% MgCl '6H O, 2% poly (20) ethyleneglycol ester of oleicacid softener, and 5% (solids) of the 49% betaine/ 31% AA/20% MAcopolymer of part (a) hereof. This pad-bath solution is applied to 65%Dacron/35% cotton shirting fabric (No. 7406 Testfabrics, Inc.) to about80% fabric Wet pickup. The fabric is then dried at 110 C. for 5 min. ona tenter frame and then cured at 160 C. for 3 min.

This procedure is then repeated with conventional carboxylic-type soilrelease emulsion polymers, Polymers 1(b) and 1(c) in Table I,substituted for the betaine Polymer 1(a).

' (c) Average soil release ratings of untreated fabric, fabric treatedonly with DMDHEU durable press resin, and fabric treated in a one-bathprocess with DMDHEU and the betaine polymer, Polymer 1(a), are listed inTable I. Also included in Table I are soil release ratings of fabricstreated in a one-bath process with DMDHEU and conventional carboxylicsoil release polymers which do not contain betaine. V

Soil release ratings of fabric treated with the betaine polymer aresubstantially better than those of untreated and DMDHEU-treated fabric.Not only is the initial soil release rating of fabric treated with thebetaine polymer superior to those of fabrics treated with conventionalcarbo xylic soil-release polymers. After about 1020 washes, so much ofthe conventional soil-release polymers has 14 been removed in washingthat soil release ratings are only slightly better than those ofuntreated fabric whereas soil release ratings of fabrics treated withbetaine polymer are substantially better than untreated fabric up toabout 30 washes. It is clear, then, that the betaine polymer 18substantially more durable to washing than the conventional carboxylicsoil-release polymers.

Table I shows the soil-release ratings of the treated fabrics at variousstages of the life of the fabric after treatment, that is, the life asdetermined by the number of washings to which the fabric is subjectedbefore the sta1n-test, the rating obtained from which is reported.

TABLE I Average soil release rating Washes before Polymer evaluation bystain-test Untreated DMDHEU 1(a) 1(b)-' 1(0) 1N0 polymer; 2 Polymer 1(a)=49% betaine/31% AA/20% MA.

3 Polymer 1(b) =80% methacrylic acid (MAA)/20% ethyl acrylate (EA). 4Polymer 1(c) =33% MAA/l7% methyl methacrylate (MAA)/50% EA.

((1) Similarly improved soil release properties are obtained when thecopolymer used in part (b) above is replaced with each of the followingcopolymers:

(A) N-(Z-carboxyethyl) inner salt of diethylaminoethyl acrylate (45methacrylic acid (30%) and butyl acrylate (25% (B) 60%N-(Z-carboxypropyl) inner salt of 3-dimethylaminopropyl acrylate, 15%itaconic acid, and 25% styrene.

(C). 55% N-(2-carboxyethyl) inner salt of morpholinoethyl methacrylate,25% monoethyl maleate, 20% acrylonitrile.

(D) 60% N-(Z-carboxyethyl) inner salt of piperidinoethyl methacrylate,25% acrylic acid, and 15 vinyltoluene.

(E) 50% N-(Z-carboxyethyl) inner salt of piperazinoethyl acrylate, 30%acrylic acid, 5% styrene, and 15% methacrylamide.

(F) 45% N-(Z carboxyethyl) inner salt of N-(di-"methylaminoethyl)-methacrylamide, 30% acrylic acid, 25 methyl acrylate.

(G) 61% l I-(2-carboxyethyl) inner salt ofN-(diethylaminoethyl)-acrylamide, 35% monomethylitaconate, 4%N-methylolacrylamide.

(H) 50% N (4-carboxyethyl) inner salt ofN-(diethylaminoethyD-acrylamide, 30% acrylic acid, and 20% methylacrylate.

(I) 54% N-(3-su1fonopropyl) inner salt of dimethylaminoethylmethacrylate (see Ex. 1 of Hwa Ser. No. 316,163 filed Oct. 14, 1963, 27%acrylic acid, 19% ethyl acrylate.

(J) 60% N-(3-sulfonopropyl) inner salt ofN-(3-dimethylaminopropyl)-methacrylamide (Ex. 2 of Ser. No. 316,163supra), 20% acrylic acid, 20% styrene.

(K) 48% N-(2-sulfatopropyl) inner salt ofN-(Z-dimethylaminoethyl)-acrylamide (Ex. 6 of Ser. No. 3 16,163 supra),20% acrylic acid, 32% methyl acrylate.

(L) 52% N-(2-sulfatoethyl) inner salt of dimethylaminoethyl methacrylate(Ex. 5 of Ser. No. 316,163

supra), 28% methacrylic acid, 10% methyl methacrylate,

15 (N) 10% N-(Z-sulfatoethyl) inner salt of dimethylaminoethylmethacrylate, acrylic acid, 15% acrylamide, 70% ethyl acrylate.

(O) 85% =N-(2-carboxyethyl) inner salt of dimethylaminoethylmethacrylate, 5% acrylic acid, dimethylaminoethyl methacrylate.

Example 2 A series of polymers of varying betaine, acrylic acid, andmethyl acrylate content prepared by the procedure described in Example1(a) using different proportions of the same monomers are substitutedfor the betaine polymer in the procedure of Example 1(b). The pH of thepolymers is adjusted to 4.5 before use. Average soil release ratings arelisted in Table II.

TABLE II Average soil release rating Polymer 2(a) 2(b) 2(0) 2(d) Washesbefore stain-test:

Polymer 2(a) =61.4% betaine/38.6% AA.

Polymer 20)) =40% MA/37% betaine/23% AA. Polymer 2(c)=50% MA/31%betaine/19% AA. Polymer 2(d) =60% Mix/25% betaine/% AA.

Example 3 (a) A series of copolymers containing betaine, acrylic acid,and methyl methacrylate (MMA) or ethyl acrylate (EA) are prepared asdescribed in Example 1(a) and are substituted in the pad-bathformulation for the betaine polymer used in the procedure of Example1(b). Average soil release ratings are listed in Table IH.

alolymer 3(a)=20% MMA/58% betaine/% AA/2% DMAEMA, pH= pglggier 3fl0)=30%M1\4A/51% betaine/17.5% AA/1.5% DMAEMA, 5filolymer 3(c)=40% MMA/44%betaine/15% Art/1% DMAEMA, pH= plgglirgier 3(d)=50% MMA/36.5%betaine/12.5% AA/l% DMAEMA,

Polymer 3(e) =20% IDA/58% betaine/20% Ark/2% DMAEMA, pH=4.5. Polymer3(i)=40% EA/44% betaine/15% AA/l% DMAEMA, pH= 4.5.

(b) A homopolymer of the betaine used in Example 1 is substituted forthe copolymer in the pad-bath formulation of Mb) (5% being used as inEx. 1(b)) and a Dacron/cotton fabric is treated with the resultingcomposition in the same manner as in Example 1(b).. After 15 Washes, thetreated fabricshowed progressive improvement in soil-release propertieson each succeeding wash.

Example 4 The procedure of Example 1(b) is repeated with the exceptionthat 100% cotton fabric (80 cotton fabric from Testfabrics, 'Inc.) istreated rather than 65% Dacron/ 35% cotton fabric. Average soil-releaseratings are listed in Table IV, together with those of an untreatedcontrol fabric and the same cotton fabric treated only with DMDHEUdurable-press resin.

TABLE IV' Average soil release rating Polymer Untreated DMDHEU 1 1(a) 22(a) 3 1 N0 polymer. 2 Polymer 1(a) =49% betaine/31% Ark/20% MA, pH=4.5.3 Polymer 2(a)=6l.4% betaine/38.6 AA, pH=6.0.

Example 5 The procedure of Example 1 is repeated with the exception thatthe pH of the polymer is adjusted with NaOH to pH 3.5 or 6.0 beforemixing with the other components of the bath. Average soil releaseratings are listed in Table V. If the polymer is adjusted to pH 6.0,initial soil release is excellent but durability is poor. If pH isadjusted to 3.5, durability is excellent but soil release is onlymoderately good throughout the series of 29' Washes. These results maybe compared with the excellent results obtained in Example 1 Where thepH of the polymer is adjusted to 4.5. The results of this exampleemphasize the necessity of applying polymer at the proper pH in order toobtain optimum soil release and durability to washing.

TABLE V Average soil release rating pH=3.5 pH= 6.0

Washes before stain test:

Example 6 TABLE VI Washes before Average soil stain-test: releaseratings 0 4.9 l I. 4.6 4 4.5 9 .y l 14 l 3.0 19 2.7

EXAMPLE 7 The procedure of Example 1(b) is repeated except that adimethylol methoxyethyl carbamate durable press reagent is substitutedon an equal solids basis for DMDHEU in the pad-bath formulation ofExample 1(b). Average soil release ratings are listed in Table VII.

TABLE VII Washes before Average soil stain-test: release rating 4.4 14.1 4 4.3

EXAMPLE 8 The 37% betaine/23% AA/40% MA and 25% betaine/ 15% AA/60% MAcopolymers used in Example 2 are adjusted to pH 6.0 with NaOH andapplied alone to 65% Dacron/35% cotton shirting (i.e., without DMDHEU)fabric using the pad-dry cure procedue described in Example 1(b).Average soil release ratings are listed in Table VIII.

TABLE VIII Average soil release rating Polymer 2(b) 2(d) Washes beforestain test:

Polymer 2(b) =37% betaine/23% AA/40% MA, pH=6.0. Polymer 2((1) =25%betaine/15% Ark/60% MA, pH=6.0.

EXAMPLE 9 An 18% betaine/ 11.6% AA/ 70% MA copolymer is prepared inaqueous solution adjusted to pH 2.5 with sulfuric acid by a gradualaddition redox process with 0.2% ammonium persulfate, 0.1% sodiummetabisulfite and 1% emulsifier. The final product contains 19.8% solidsand the viscosity is 29.5 cps. The pH of the copolymer is adjusted to6.2 with NaOH before use. The procedure of Example 1(b) is repeatedexcept this polymer is substituted for the betaine polymer used inExample 1(b). Average soil release ratings are listed in Table IX.

TABLE IX Washes before I Average soil stain-test: release rating 0 3.9 13.9 4 3.3 9 3.6 14 3.0 9 2.8

EXAMPLE 10 TABLE X Surface resistivity at 76 F. (ohms) 9% relative40%relative humidity humidity Treated fabric 4. 8X10 1. 1X10 Untreatedfabric 2. 9X10 2. 6X10 EXAMPLE 11 The resistance of fabric treated withbetaine polymer in accordance with Example 1(b) to pickup of dry soil isevaluated as follows. Separate 4 in. x 4 in. cuttings of treated anduntreated fabric are tumbled 20 min, at 76 F. in glass jars containing 6rubber balls and 0.1 g. of vacuum cleaner soil which had been filteredthrough a TABLE XI Treated Untreated fabric fabric Soil pickup, (g.):

Soiled 0. 0069 0. 0092 Soil transfer 0.0022 0. 0025 Reflectance (K/S)(0.000=white):

Initial 0. 012 0. 009 Soiled 0.070 0.105 Soil transfer 0.021 0.025

EXAMPLE 12 Nylon taffeta fabric (N0. 306A, Testfabrics, Inc.) is treatedwith the 49% betaine/ 31% acrylic acid/ 12% methyl acrylate copolymer ofExample 1(a) using the paddry-cure process described in Example 1(b)except the pad-bath solution contains only the copolymer at 5%concentration. A 2.0% add-on (weight polymer/weight fabric) is obtained.At 76 F., 9% relative humidity, surface resistivity of the treatedfabric is 4.4 10 ohms, while that of an untreated control fabric is 1.4x10 ohms.

Average soil release rating of treated fabrics is 5.0 compared with 4.5for that of an untreated control fabric.

EXAMPLE 13 The process of Example 1(b) is repeated except a fabric of anacrylonitrile polymer (Orlon) (Type 81, No. 801 from Testfabrics, Inc.)is substituted for the polyester/cotton fabric and the reagents otherthan polymer and water are omitted from the pad-bath formulation.Average soil release rating of treated fabric is 4.8 compared with 3.0for an untreated control fabric.

We claim:

1. A method for modifying a textile material which comprises applying tothe material a liquid medium containing:

(a) an addition polymer of 5% to by weight of a monomer of the formula 0R 11.0:0 (R) Z A(O-A) n-I I?AR-O i. wherein n is zero or an integerhaving a value of 1 to 10,

R is H or methyl,

A is an alkylene group having 2 to 6 carbon atoms, at least two of whichextend in a chain between the quaternary nitrogen atom and the adjoinedZ radical when n is 0, and A, when n is 1 to 10, is a (C -C alkylenegroup having at least 2 carbon atoms extending in a chain between 0atoms or between an O atom and the adjoined N atom or Z radical,

R is (C -C )alkyl, or

R and R may together form with the N atom a 5- to 6-atom ring, in whichthe atoms are C, N, or 0, such as the morpholino, piperidino, andpiperazino groups,

A is a divalent saturated aliphatic hydrocarbon radical, such asalkylene, having 1 to 4 carbon atoms, and

wherein m is 1 or 2,

(b) a thermosetting aminoplast condensate, and

(c) an acidic catalyst for setting the condensate, the application beingcontrolled to deposit about 0.25 to 30% by weight of dry polymer on theweight of fibers in the textile, drying the treated textile and heatingit to about 130 to 200 C. to set the composition thereon.

2. A method according to claim 1 for imparting soil release and durablepress characteristics wherein the textile material comprises linearpolyester fibers and the aqueous composition contains: about 2.5 to 40%by weight of the addition polymer, about 2 to 30% by weight of thethermosetting aminoplast condensate, and up to 15%, based on the weightof the condensate, of an acidic curing catalyst for the condensate.

3. A method according to claim 1 in which the addition polymer is acopolymer of 5 to 100% by weight of at least one monomer of Formula I, 0to 95% by weight of at least one u,fl-monoethylenically unsaturatedacid, and 0 to 95% by weight at least one other compolymerizablemonoethylenically unsaturated monomer.

4. A method according to claim 1 in which the addition polymer is acopolymer of 20 to 60% by weight of at least one monomer of Formula Iwherein R is 15 to 50% by weight of at least one u,B-monoethylenicallyunsaturated acid, and to 60% by Weight of at least one othercopolymerizable monoethylenically unsaturated monomer having a group ofthe formula H C=O 5. A method according to claim 1 in which the textilematerial is a cellulosic fiber-containing material.

6. A method according to claim 1 in which the textile material is ablend of cotton and polyethylene glycol terephthalate fibers.

7. A textile material prepared according to claim 1.

8. A method according to claim 2 in which "the addition polymer is acopolymer of 20-60% by weight of the N-(Z-carboxyethyl) inner salt ofdimethylaminoethyl methacrylate, 1550% by Weight of acrylic acid, and10-60% by weight of methyl acrylate.

9. A textile material prepared according to claim 3.

10. A textile material having soil-release and durable presscharacteristics prepared according to claim 4.

References Cited UNITED STATES PATENTS 3,497,482 2/1970 HWa 117-139.5 X3,322,569 5/1967 Faulhaber et a1. 117-1394 3,377,249 4/1968 Marco 8115.63,405,003 10/1968 DePaolo et a1. 117-139.5 3,459,716 8/1969 Schaefer eta1. l17139.5 X 3,535,141 10/1970 Marco ll7l39.5 X 3,280,179 10/1966Ernst 2'60501.12

WILLIAM D. MARTIN, Primary Examiner T. G. DAVIS, Assistant Examiner U.S.Cl. X.R.

1l7l39.4, 139.5 A, 143 A, 138.8 N, 138.8 UA

